EP0413205A2 - Dihydroxydiphenylcycloalkane-based polysiloxane-polycarbonate block copolymers - Google Patents
Dihydroxydiphenylcycloalkane-based polysiloxane-polycarbonate block copolymers Download PDFInfo
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- EP0413205A2 EP0413205A2 EP90114809A EP90114809A EP0413205A2 EP 0413205 A2 EP0413205 A2 EP 0413205A2 EP 90114809 A EP90114809 A EP 90114809A EP 90114809 A EP90114809 A EP 90114809A EP 0413205 A2 EP0413205 A2 EP 0413205A2
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- polydiorganosiloxane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/186—Block or graft polymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
- C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
Definitions
- the invention relates to thermoplastic polydiorganosiloxane-polycarbonate block copolymers based on dihydroxydiphenylcycloalkanes of the formula (I) wherein R1, R2, R3, R4 independently of one another are hydrogen, halogen, preferably chlorine or bromine, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C10-aryl and C7-C12-aralkyl, preferably phenyl-C1-C4-alkyl , especially benzyl, n 2 or 3 and the radicals R5 independently of one another are hydrogen, or C1-C12-alkyl, with the proviso that at least one of the radicals R5 is not hydrogen.
- R1, R2, R3, R4 independently of one another are hydrogen, halogen, preferably chlorine or bromine, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C10-aryl and C7-C12
- R5 is preferably a straight-chain C1-C5 alkyl radical or a branched C3-C8 alkyl radical.
- the polydiorganosiloxane-polycarbonate block copolymers are distinguished by heat resistance, strength, good UV stability and toughness.
- Suitable ⁇ , ⁇ -bishydroxy-aryloxy-polydiorganosiloxanes a) are e.g. known from U.S. Patent 3,419,634.
- R and R ' are independent of one another. They are preferably C1-C20 alkyl, C2-C6 alkenyl, C6-C14 aryl. Halogenated means partially or completely chlorinated, brominated or fluorinated.
- R and R ′ are particularly preferably methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, chloromethyl, trifluoropropyl, perfluorobutyl and perfluorooctyl.
- Diphenols (b) are diphenols of the formula (I) and formula (III) given above HO-Ar o -OH (III), wherein Ar o are the same or different arylene radicals, preferably having 6 to 30 carbon atoms.
- diphenols of the formula (III) are: Hydroquinone Resorcinol Dihydroxydiphenyls Bis (hydroxyphenyl) alkanes Bis (hydroxyphenyl) cycloalkanes other than formula (I) Bis (hydroxyphenyl) sulfides Bis (hydroxyphenyl) ether Bis (hydroxyphenyl) sulfoxides Bis (hydroxyphenyl) sulfones and ⁇ , ⁇ -bis (hydroxyphenyl) diisopropylbenzenes as well as corresponding nuclear alkylated and nuclear halogenated compounds.
- These and other suitable diphenols are described, for example, in US Pat. Nos.
- Preferred diphenols of the formula (III) are: wherein X 'is a single bond, -CH2-, -C (CH3) 2-, -O-, -S-, mean and Y1 to Y4 are the same or different and are hydrogen, C1-C4-alkyl, preferably methyl or halogen, preferably chlorine or bromine.
- Preferred diphenols are 2,2-bis (4-hydroxyphenyl) propane 1,1-bis (4-hydroxyphenyl) cyclohexane 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane Bis (3,5-dimethyl-4-hydroxyphenyl) methane Bis (4-hydroxyphenyl) sulfide.
- One or more diphenols of the formula (I) and optionally one or more diphenols of the formula (III) can be used.
- Diphenols of the formula (I) can be prepared in a manner known per se by condensation of phenols of the formula (V) and ketones of the formula (VI) are prepared, wherein in the formulas (V) and (VI) X, R1, R2, R3, R4, R5 and n have the meaning given for the formula (I).
- Phenols of the formula (VII) are particularly preferred as chain terminators
- the branching agents d) used are those with three or more than three functional groups, in particular those with three or more than three phenolic hydroxyl groups bar, in the usual amounts of 0.05 to 2 mol%, based on the incorporated diphenols.
- Some of the compounds which can be used with three or more than three phenolic hydroxyl groups are 2,4-bis (4-hydroxyphenyl-isopropyl) phenol, 2,6-bis (2'-hydroxy-5'-methyl-benzyl) -4 -methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane and 1,4-bis (4,4'-dihydroxytriphenyl-methyl) -benzene.
- Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis- (4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 3,3-bis- (4-hydroxy-3) -methyl-phenyl) -2-oxo-2,3-dihydroindole.
- Suitable organic solvents for the two-phase interfacial polycondensation are those known for the production of aromatic polycarbonates, such as, for example, methylene chloride or chlorobenzene.
- Their amounts are preferably chosen so that the two-phase interfacial polycondensation takes place in 5 to 20% solution in the organic solvent, preferably 10 to 15% solution.
- Suitable basic compounds for the formation of the aqueous alkaline phase are solutions of LiOH, NaOH, KOH, Ca (OH) 2 and / or Ba (OH) 2 in water.
- the volumes of the aqueous alkaline phase and the entire organic phase are preferably the same.
- the pH of the aqueous phase during the reaction is 9 to 14, preferably 12 to 13.
- Suitable catalysts for two-phase interfacial polycondensation are the tertiary aliphatic amines known for polycarbonate synthesis, such as trimethylamine, triethylamine, n-tripropylamine, n-tributylamine or N-ethylpiperidine; if necessary, quaternary ammonium salts such as tetrabutylammonium bromide can also be used.
- quaternary ammonium salts such as tetrabutylammonium bromide can also be used.
- 0.2 to 5 mol% for tetramethyl-substituted diphenols 5 to 10 mol% catalyst, based in each case on the total amount of diphenols b), can be used.
- the amounts of diphenol b) and ⁇ , ⁇ -bishydroxyaryloxy-polydiorganosiloxane a) depend on the desired content of poly (diorganosiloxane) units in the block copolymer.
- the reaction of the reactants is usually quantitative.
- the ⁇ , ⁇ -bishydroxyaryloxypolydiorganosiloxanes and the chain terminator can be added in the two-phase interfacial polycondensation together with the diphenols b) before the phosgene introduction or separately during or after the phosgene introduction, but in any case before the addition of the polycondensation catalyst.
- carbonate donor for the two-phase polycondensation serve in a known manner carbonic acid halides, in particular carbonic acid chlorides, such as phosgene, COBr2, or the bischlorocarbonate of diphenols in an appropriate amount, with less than 1/2 diphenol being used per mole of halogen carbonic acid group.
- the polydiorganosiloxane-polycarbonate block copolymers can be separated from the reaction mixtures like aromatic polycarbonates.
- the organic phase containing the block copolymer is first separated off, washed and then the block copolymer is isolated by evaporating the solution, an evaporation extruder preferably being used as the final stage of the workup process.
- thermoplastic block copolymers according to the invention can contain anti-aging agents which significantly increase their stability.
- anti-aging agents e.g. Carbon black, kieselguhr, kaolin, clays, CaF2, CaCO3, aluminum oxides, glass fibers and inorganic pigments can be added both as fillers and as nucleating agents. They can also use the mold release agents customary for polycarbonate, e.g. Glycerol stearate.
- the polydiorganosiloxane-polycarbonate block copolymers are thermoplastic molding compositions which can be used wherever their essential properties, heat resistance, strength, toughness and UV stability are required.
- the polydiorganosiloxane-polycarbonate block copolymers can also be used with other, siloxane-free, thermoplastic polycarbonates based on diphenols of the formula (I) and (III) thermoplastic molding compositions form. These polycarbonates have average molecular weights M w (weight average, determined by ultracentrifugation or scattered light measurement) from 10,000 to 300,000. The content of polydiorganosiloxane structural units in the mixture is also 25 to 1.0% by weight, based in each case on the total weight of the mixture.
- Polydiorganosiloxane-polycarbonate block copolymers with a content of polydiorganosiloxane structural units of more than 25% by weight, preferably 40 to 60% by weight, are also suitable for producing such mixtures M w suitable from 15,000 to 80,000.
- Such polydiorganosiloxane-polycarbonate block copolymers can be prepared by a suitable choice of the amount of starting materials.
- the polydiorganosiloxane-polycarbonate block copolymers according to the invention can be used to produce moldings of any type by known processes.
- moldings can be produced by extrusion or injection molding.
- moldings that can be produced are body parts and housing parts, e.g. for electrical devices and equipment such as household appliances, building boards and foils.
- the impact strength was determined according to ISO 180 on flat bars (80 mm x 10 mm x 4 mm), the heat resistance according to the Vicat (B) method according to DIN 53 460 / ISO 360.
Abstract
Polydiorganosiloxan-Polycarbonat-Blockcopolymere auf Basis von Dihydroxydiphenylcycloalkanen der Formel (I) <IMAGE> worin R¹, R², R³, R<4> unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom, C1-C8-Alkyl, C5-C6-Cycloalkyl, C6-C10-Aryl und C7-C12-Aralkyl, bevorzugt Phenyl-C1-C4-Alkyl, insbesondere Benzyl, n 2 oder 3 und die Reste R<5> unabhängig voneinander Wasserstoff, oder C1-C12-Alkyl bedeuten, mit der Maßgabe, daß mindestens einer der Reste R<5> ungleich Wasserstoff ist, mit mittlerem Molekulargewicht Mw (Gewichtsmittel) von 10.000 bis 300.000, (ermittelt durch Ultrazentrifugation oder Streulichtmessung), und einem Gehalt an Polycarbonat, das Dihydroxydiphenylcycloalkane der Formel I und gegebenenfalls andere Diphenole einkondensiert enthält, von 75 Gew.-% bis 99,0 Gew.-% und einem Gehalt an Polydiorganosiloxan mit einem Polymerisationsgrad von Pn 5 - 300, von 25 Gew.-% bis 1 Gew.-%.Polydiorganosiloxane-polycarbonate block copolymers based on dihydroxydiphenylcycloalkanes of the formula (I) <IMAGE> wherein R¹, R², R³, R <4> independently of one another are hydrogen, halogen, preferably chlorine or bromine, C1-C8-alkyl, C5-C6-cycloalkyl , C6-C10-aryl and C7-C12-aralkyl, preferably phenyl-C1-C4-alkyl, in particular benzyl, n 2 or 3 and the radicals R <5> independently of one another are hydrogen, or C1-C12-alkyl with which Provided that at least one of the radicals R 5 is not hydrogen, with an average molecular weight Mw (weight average) of 10,000 to 300,000 (determined by ultracentrifugation or scattered light measurement), and a content of polycarbonate, the dihydroxydiphenylcycloalkanes of the formula I and optionally other diphenols contains in condensed form from 75% by weight to 99.0% by weight and a content of polydiorganosiloxane with a degree of polymerization of Pn 5-300, from 25% by weight to 1% by weight.
Description
Gegenstand der Erfindung sind thermoplastische Polydiorganosiloxan-Polycarbonat-Blockcopolymere auf Basis von Dihydroxydiphenylcycloalkanen der Formel (I)
R¹, R², R³, R⁴ unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom, C₁-C₈-Alkyl, C₅-C₆-Cycloalkyl, C₆-C₁₀-Aryl und C₇-C₁₂-Aralkyl, bevorzugt Phenyl-C₁-C₄-Alkyl, insbesondere Benzyl,
n 2 oder 3 und
die Reste R⁵ unabhängig voneinander Wasserstoff, oder C₁-C₁₂-Alkyl bedeuten, mit der Maßgabe, daß mindestens einer der Reste R⁵ ungleich Wasserstoff ist.The invention relates to thermoplastic polydiorganosiloxane-polycarbonate block copolymers based on dihydroxydiphenylcycloalkanes of the formula (I)
R¹, R², R³, R⁴ independently of one another are hydrogen, halogen, preferably chlorine or bromine, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl and C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl , especially benzyl,
n 2 or 3 and
the radicals R⁵ independently of one another are hydrogen, or C₁-C₁₂-alkyl, with the proviso that at least one of the radicals R⁵ is not hydrogen.
Bevorzugt ist R⁵ ein geradkettiger C₁-C₅-Alkylrest oder ein verzweigter C₃-C₈-Alkylrest.R⁵ is preferably a straight-chain C₁-C₅ alkyl radical or a branched C₃-C₈ alkyl radical.
Die erfindungsgemäßen Polydiorganosiloxan-Polycarbonat-Blockcopolymere zeichnen sich durch Wärmeformbeständigkeit, Festigkeit, gute UV-Stabilität und Zähigkeit aus.The polydiorganosiloxane-polycarbonate block copolymers are distinguished by heat resistance, strength, good UV stability and toughness.
Polydiorganosiloxan-Polycarbonat-Blockcopolymere sind grundsätzlich bekannt (vgl. US-PS 3 189 662, 3 419 634, DE-OS 3 334 782, 3 506 472, EP-A 122 535, 135 794).Polydiorganosiloxane-polycarbonate block copolymers are known in principle (cf. US Pat. No. 3,189,662, 3,419,634, DE-OS 3,334,782, 3,506,472, EP-A 122,535, 135,794).
Die erfindungsgemäßen thermoplastischen Polydiorganosiloxan-Polycarbonat-Blockcopolymere besitzen ein mittleres Molekulargewicht
- a) α,ω-Bishydroxyaryloxy-polydiorganosiloxanen mit einem Polymerisationsgrad Pn von 5 bis 300, vorzugsweise von 20 bis 160, vorzugsweise solchen der Formel (II),
- b) Diphenolen der Formel (I) (5 bis 100 Mol-%, bevorzugt 10 bis 80 Mol-%) und gegebenenfalls zusätzlich solchen der Formel (III) (0 bis 95 Gew.-%, bevorzugt 90 bis 20 Gew.-%), gegebenenfalls
- c) Kettenabbrechern und gegebenenfalls
- d) Verzweigern,
- a) α, ω-bishydroxyaryloxy-polydiorganosiloxanes with a degree of polymerization Pn of 5 to 300, preferably 20 to 160, preferably those of the formula (II),
- b) diphenols of the formula (I) (5 to 100 mol%, preferably 10 to 80 mol%) and optionally additionally those of the formula (III) (0 to 95% by weight, preferably 90 to 20% by weight ), possibly
- c) chain terminators and optionally
- d) branching,
Geeignete α,ω-Bishydroxy-aryloxy-polydiorganosiloxane a) sind z.B. aus US-PS 3 419 634 bekannt.Suitable α, ω-bishydroxy-aryloxy-polydiorganosiloxanes a) are e.g. known from U.S. Patent 3,419,634.
Bevorzugte α,ω-Bishydroxyaryloxy-polydiorganosiloxane sind solche der Formel (II)
Ar den Rest eines Diphenols der Formel (I) oder der Formel (III) ohne die beiden Hydroxylgruppen und
R und R′ lineares Alkyl, verzweigtes Alkyl, Alkenyl, halogeniertes lineares Alkyl, halogeniertes verzweigtes Alkyl, Aryl oder halogeniertes Aryl, vorzugsweise Methyl bedeuten,
und
o, p, q ganze Zahlen bedeuten, für die gilt n = o+p+q = 5 bis 300, vorzugsweise 20 bis 160.Preferred α, ω-bishydroxyaryloxy-polydiorganosiloxanes are those of the formula (II)
Ar is the residue of a diphenol of the formula (I) or of the formula (III) without the two hydroxyl groups and
R and R ′ represent linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl, preferably methyl,
and
o, p, q are integers, for which n = o + p + q = 5 to 300, preferably 20 to 160.
In Formel (II) sind die Reste R und R′ unabhängig voneinander. Sie sind bevorzugt C₁-C₂₀-Alkyl, C₂-C₆-Alkenyl, C₆-C₁₄-Aryl. Halogeniert bedeutet teilweise oder vollständig chloriert, bromiert oder fluoriert. Besonders bevorzugt ist R und R′ Methyl, Ethyl, Propyl, n-Butyl, tert.-Butyl, Vinyl, Phenyl, Naphthyl, Chlormethyl, Trifluorpropyl, Perfluorbutyl und Perfluoroctyl.In formula (II) the radicals R and R 'are independent of one another. They are preferably C₁-C₂₀ alkyl, C₂-C₆ alkenyl, C₆-C₁₄ aryl. Halogenated means partially or completely chlorinated, brominated or fluorinated. R and R ′ are particularly preferably methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, chloromethyl, trifluoropropyl, perfluorobutyl and perfluorooctyl.
Diphenole (b) sind Diphenole der oben angegebenen Formel (I) und der Formel (III)
HO-Aro-OH (III),
worin
Aro gleiche oder verschiedene Arylenreste mit vorzugsweise 6 bis 30 C-Atomen sind.Diphenols (b) are diphenols of the formula (I) and formula (III) given above
HO-Ar o -OH (III),
wherein
Ar o are the same or different arylene radicals, preferably having 6 to 30 carbon atoms.
Beispiele für Diphenole der Formel (III) sind:
Hydrochinon
Resorcin
Dihydroxydiphenyle
Bis-(hydroxyphenyl)-alkane
Bis-(hydroxyphenyl)-cycloalkane außer der Formel (I)
Bis-(hydroxyphenyl)-sulfide
Bis-(hydroxyphenyl)-ether
Bis-(hydroxyphenyl)-sulfoxide
Bis-(hydroxyphenyl)-sulfone und
α,ω-Bis-(hydroxyphenyl)-diisopropylbenzole
sowie entsprechende kernalkylierte und kernhalogenierte Verbindungen. Diese und weitere geeignete Diphenole sind z.B. in den US-PS 3 028 365 und 2 999 846 und in den DE-OS 1 570 703, 2 036 052, 2 063 050, 2 211 957, der FR-PS 561 518 und in "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" beschrieben.Examples of diphenols of the formula (III) are:
Hydroquinone
Resorcinol
Dihydroxydiphenyls
Bis (hydroxyphenyl) alkanes
Bis (hydroxyphenyl) cycloalkanes other than formula (I)
Bis (hydroxyphenyl) sulfides
Bis (hydroxyphenyl) ether
Bis (hydroxyphenyl) sulfoxides
Bis (hydroxyphenyl) sulfones and
α, ω-bis (hydroxyphenyl) diisopropylbenzenes
as well as corresponding nuclear alkylated and nuclear halogenated compounds. These and other suitable diphenols are described, for example, in US Pat. Nos. 3,028,365 and 2,999,846 and in DE-OS 1,570,703, 2,036,052, 2,063,050, 2,211,957, FR-PS 561,518 and in " H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 ".
Bevorzugte Diphenole der Formel (III) sind:
X′ eine Einfachbindung, -CH₂-, -C(CH₃)₂-, -O-, -S-,
Y¹ bis Y⁴ gleich oder verschieden sind und Wasserstoff, C₁-C₄-Alkyl, vorzugsweise Methyl oder Halogen, vorzugsweise Chlor oder Brom, bedeuten. Bevorzugte Diphenole sind
2,2-Bis-(4-hydroxyphenyl)-propan
1,1-Bis-(4-hydroxyphenyl)-cyclohexan
2,2-Bis-(3,5-dichlor-4-hydroxyphenyl)-propan
2,2-Bis-(3,5-dibrom-4-hydroxyphenyl)-propan
2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propan
Bis-(3,5-dimethyl-4-hydroxyphenyl)-methan
Bis-(4-hydroxyphenyl)-sulfid.Preferred diphenols of the formula (III) are:
X 'is a single bond, -CH₂-, -C (CH₃) ₂-, -O-, -S-,
Y¹ to Y⁴ are the same or different and are hydrogen, C₁-C₄-alkyl, preferably methyl or halogen, preferably chlorine or bromine. Preferred diphenols are
2,2-bis (4-hydroxyphenyl) propane
1,1-bis (4-hydroxyphenyl) cyclohexane
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane
Bis (3,5-dimethyl-4-hydroxyphenyl) methane
Bis (4-hydroxyphenyl) sulfide.
Es können ein oder mehrere Diphenole der Formel (I) und gegebenenfalls daneben ein oder mehrere Diphenole der Formel (III) eingesetzt werden.One or more diphenols of the formula (I) and optionally one or more diphenols of the formula (III) can be used.
Diphenole der Formel (I) können in an sich bekannter Weise durch Kondensation von Phenolen der Formel (V)
Als Kettenabbrecher c) sind aromatische Verbindungen mit nur einer funktionellen Gruppe wie aromatische Säurehalogenide oder Phenole, insbesondere die gebräuchlichen Phenole wie p-tert.-Butylphenol, p-Chlorphenol, 2,4,6-Tribromphenol und Phenol in Mengen einsetzbar, die sich nach dem gewünschten Molekulargewicht der Blockcopolymeren bestimmen. Besonders bevorzugt sind als Kettenabbrecher Phenole der Formel (VII)
Im allgemeinen werden 0,5 Mol-% bis 10,0 Mol-%, bezogen auf eingesetzte Diphenole, eingesetzt.In general, 0.5 mol% to 10.0 mol%, based on the diphenols used, are used.
Als Verzweiger d) sind solche mit drei oder mehr als drei funktionellen Gruppen, insbesondere solche mit drei oder mehr als drei phenolischen Hydroxylgruppen einsetz bar, in den üblichen Mengen von 0,05 bis 2 Mol-%, bezogen auf eingebaute Diphenole.The branching agents d) used are those with three or more than three functional groups, in particular those with three or more than three phenolic hydroxyl groups bar, in the usual amounts of 0.05 to 2 mol%, based on the incorporated diphenols.
Einige der verwendbaren Verbindungen mit drei oder mehr als drei phenolischen Hydroxylgruppen sind 2,4-Bis-(4-hydroxyphenyl-isopropyl)-phenol, 2,6-Bis-(2′-hydroxy-5′-methyl-benzyl)-4-methylphenol, 2-(4-Hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propan und 1,4-Bis-(4,4′-dihydroxytriphenyl-methyl)-benzol. Einige der sonstigen trifunktionellen Verbindungen sind 2,4-Dihydroxybenzoesäure, Trimesinsäure, Cyanurchlorid und 3,3-Bis-(4-hydroxyphenyl)-2-oxo-2,3-dihydroindol sowie 3,3-Bis-(4-hydroxy-3-methyl-phenyl)-2-oxo-2,3-dihydroindol.Some of the compounds which can be used with three or more than three phenolic hydroxyl groups are 2,4-bis (4-hydroxyphenyl-isopropyl) phenol, 2,6-bis (2'-hydroxy-5'-methyl-benzyl) -4 -methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane and 1,4-bis (4,4'-dihydroxytriphenyl-methyl) -benzene. Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis- (4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 3,3-bis- (4-hydroxy-3) -methyl-phenyl) -2-oxo-2,3-dihydroindole.
Geeignete organische Lösungsmittel für die Zweiphasengrenzflächenpolykondensation sind die für die Herstellung aromatischer Polycarbonate bekannten wie beispielsweise Methylenchlorid oder Chlorbenzol.Suitable organic solvents for the two-phase interfacial polycondensation are those known for the production of aromatic polycarbonates, such as, for example, methylene chloride or chlorobenzene.
Ihre Mengen werden vorzugsweise so gewählt, daß die Zweiphasengrenzflächenpolykondensation in 5 bis 20 %iger Lösung im organischen Lösungsmittel, vorzugsweise 10 bis 15 %iger Lösung, abläuft.Their amounts are preferably chosen so that the two-phase interfacial polycondensation takes place in 5 to 20% solution in the organic solvent, preferably 10 to 15% solution.
Geeignete basische Verbindungen für die Bildung der wäßrigen alkalischen Phase sind Lösungen von LiOH, NaOH, KOH, Ca(OH)₂ und/oder Ba(OH)₂ in Wasser.Suitable basic compounds for the formation of the aqueous alkaline phase are solutions of LiOH, NaOH, KOH, Ca (OH) ₂ and / or Ba (OH) ₂ in water.
Bei der Zweiphasengrenzflächenpolykondensation sind die Volumina von wäßrig-alkalischer Phase und gesamter organischer Phase vorzugsweise gleich.In the case of two-phase interfacial polycondensation, the volumes of the aqueous alkaline phase and the entire organic phase are preferably the same.
Der pH-Wert der wäßrigen Phase ist während der Reaktion 9 bis 14, vorzugsweise 12 bis 13.The pH of the aqueous phase during the reaction is 9 to 14, preferably 12 to 13.
Geeignete Katalysatoren für die Zweiphasengrenzflächenpolykondensation sind die für die Polycarbonatsynthese bekannten tertiären aliphatischen Amine wie Trimethylamin, Triethylamin, n-Tripropylamin, n-Tributylamin oder N-Ethylpiperidin; gegebenenfalls können auch quartäre Ammoniumsalze wie beispielsweise Tetrabutylammoniumbromid eingesetzt werden. Es können je nach eingesetztem Diphenol 0,2 bis 5 Mol-%, für tetramethylsubstituierte Diphenole 5 bis 10 Mol-% Katalysator, bezogen jeweils auf die Gesamtmenge an Diphenolen b), eingesetzt werden.Suitable catalysts for two-phase interfacial polycondensation are the tertiary aliphatic amines known for polycarbonate synthesis, such as trimethylamine, triethylamine, n-tripropylamine, n-tributylamine or N-ethylpiperidine; if necessary, quaternary ammonium salts such as tetrabutylammonium bromide can also be used. Depending on the diphenol used, 0.2 to 5 mol%, for tetramethyl-substituted diphenols 5 to 10 mol% catalyst, based in each case on the total amount of diphenols b), can be used.
Die Mengen von Diphenol b) und α,ω-Bishydroxyaryloxy-polydiorganosiloxan a) richten sich nach dem gewünschten Gehalt an Poly(diorganosiloxan)-Einheiten im Blockcopolymeren. Die Umsetzung der Reaktanten ist normalerweise quantitativ.The amounts of diphenol b) and α, ω-bishydroxyaryloxy-polydiorganosiloxane a) depend on the desired content of poly (diorganosiloxane) units in the block copolymer. The reaction of the reactants is usually quantitative.
Die α,ω-Bishydroxyaryloxypolydiorganosiloxane und der Kettenabbrecher können bei der Zweiphasengrenzflächenpolykondensation zusammen mit den Diphenolen b) vor der Phosgeneinleitung zugegeben werden oder separat während oder nach der Phosgeneinleitung, in jedem Fall aber vor der Zugabe des Polykondensationskatalysators.The α, ω-bishydroxyaryloxypolydiorganosiloxanes and the chain terminator can be added in the two-phase interfacial polycondensation together with the diphenols b) before the phosgene introduction or separately during or after the phosgene introduction, but in any case before the addition of the polycondensation catalyst.
Als "Carbonatspender" für die Zweiphasengrenzflächenpolykondensation dienen in bekannter Weise Kohlensäurehalogenide, insbesondere Kohlensäurechloride, wie Phosgen, COBr₂, oder die Bischlorkohlensäureester von Diphenolen in entsprechender Menge, wobei jeweils pro Mol Halogen-Kohlensäure-Gruppe weniger als 1/2 Diphenol verwendet wird.As a "carbonate donor" for the two-phase polycondensation serve in a known manner carbonic acid halides, in particular carbonic acid chlorides, such as phosgene, COBr₂, or the bischlorocarbonate of diphenols in an appropriate amount, with less than 1/2 diphenol being used per mole of halogen carbonic acid group.
Die Polydiorganosiloxan-Polycarbonat-Blockcopolymeren können aus den Reaktionsmischungen wie aromatische Polycarbonate abgetrennt werden. Hierbei wird zunächst die organische, das Blockcopolymer gelöst enthaltende Phase abgetrennt, gewaschen und anschließend das Blockcopolymer durch Eindampfen der Lösung isoliert, wobei als Endstufe des Aufarbeitungsprozesses vorzugsweise ein Ausdampfextruder benutzt wird.The polydiorganosiloxane-polycarbonate block copolymers can be separated from the reaction mixtures like aromatic polycarbonates. In this case, the organic phase containing the block copolymer is first separated off, washed and then the block copolymer is isolated by evaporating the solution, an evaporation extruder preferably being used as the final stage of the workup process.
Die erfindungsgemäßen thermoplastischen Blockcopolymere können Alterungsschutzmittel enthalten, die ihre Stabilität wesentlich erhöhen. Zur Modifizierung können z.B. Ruß, Kieselgur, Kaolin, Tone, CaF₂, CaCO₃, Aluminiumoxide, Glasfasern und anorganische Pigmente sowohl als Füllstoffe als auch als Nukleierungsmittel zugesetzt werden. Ebenso können sie die für Polycarbonat üblichen Entformungsmittel, wie z.B. Glycerinstearat, enthalten.The thermoplastic block copolymers according to the invention can contain anti-aging agents which significantly increase their stability. For modification, e.g. Carbon black, kieselguhr, kaolin, clays, CaF₂, CaCO₃, aluminum oxides, glass fibers and inorganic pigments can be added both as fillers and as nucleating agents. They can also use the mold release agents customary for polycarbonate, e.g. Glycerol stearate.
Die erfindungsgemäßen Polydiorganosiloxan-Polycarbonat-Blockcopolymere sind thermoplastische Formmassen, die überall anwendbar sind, wo ihre wesentlichen Eigenschaften, Wärmeformbeständigkeit, Festigkeit, Zähigkeit und UV-Stabilität gefordert werden.The polydiorganosiloxane-polycarbonate block copolymers are thermoplastic molding compositions which can be used wherever their essential properties, heat resistance, strength, toughness and UV stability are required.
Die erfindungsgemäßen Polydiorganosiloxan-Polycarbonat-Blockcopolymeren können auch mit anderen, siloxanfreien, thermoplastischen Polycarbonaten auf Basis von Diphenolen der Formel (I) und (III) thermoplastische Formmassen bilden. Diese Polycarbonate haben mittlere Molekulargewichte
Zur Herstellung solcher Mischungen sind auch Polydiorganosiloxan-Polycarbonat-Blockcopolymere mit einem Gehalt an Polydiorganosiloxanstruktureinheiten über 25 Gew.-%, vorzugsweise 40 bis 60 Gew.-%, und
Solche Polydiorganosiloxan-Polycarbonat-Blockcopolymere können durch geeignete Wahl der Menge an Ausgangsprodukten hergestellt werden.Such polydiorganosiloxane-polycarbonate block copolymers can be prepared by a suitable choice of the amount of starting materials.
Die erfindungsgemäßen Polydiorganosiloxan-Polycarbonat-Blockcopolymeren können zur Herstellung von Formkörpern jeder Art nach bekannten Verfahren verwendet werden. Insbesondere können Formkörper durch Extrusion oder Spritzguß hergestellt werden.The polydiorganosiloxane-polycarbonate block copolymers according to the invention can be used to produce moldings of any type by known processes. In particular, moldings can be produced by extrusion or injection molding.
Beispiele für herstellbare Formkörper sind Karosserieteile und Gehäuseteile, z.B. für elektrische Geräte und Apparaturen wie Haushaltsgeräte, Bauplatten und Folien.Examples of moldings that can be produced are body parts and housing parts, e.g. for electrical devices and equipment such as household appliances, building boards and foils.
Die relativen Lösungsviskositäten wurden in Dichlormethan bei 25°C und c = 5 g/l Lösung gemessen.The relative solution viscosities were measured in dichloromethane at 25 ° C and c = 5 g / l solution.
Die Kerbschlagzähigkeit wurde nach ISO 180 an Flachstäben (80 mm x 10 mm x 4 mm) ermittelt, die Wärmeformbeständigkeit nach Methode Vicat (B) gemäß DIN 53 460/ISO 360.The impact strength was determined according to ISO 180 on flat bars (80 mm x 10 mm x 4 mm), the heat resistance according to the Vicat (B) method according to DIN 53 460 / ISO 360.
26,5 g (0,094 Mol) 1,1-Bis-(4-hydroxyphenyl)-3-methyl-cyclohexan, 6,75 g (0,17 Mol) NaOH und 385 g Wasser werden in einer Inertgas-Atmosphäre unter Rühren gelöst. Dann fügt man eine Lösung von 1,67 g des Polydimethylsiloxan-Blocks (Pn = 71) mit Bisphenol A-Endgruppen (= 5 Gew.-% SiMe₂O) und 0,22 g (2,3 mMol) Phenol in 190 ml Methylenchlorid zu. In die gut gerührte Lösung wurden bei pH 12 bis 13 und 21 bis 25°C 15,8 g (0,16 Mol) Phosgen eingeleitet. Danach werden 0,14 ml Ethylpiperidin zugegeben und noch 45 Min. gerührt. Die bisphenolatfreie wäßrige Phase wird abgetrennt, die organische Phase, nach Ansäuern mit Phosphorsäure, mit Wasser neutral gewaschen und vom Lösungsmittel befreit.
ηrel: 1.279
Tg (DSC): 211,5°C26.5 g (0.094 mol) of 1,1-bis (4-hydroxyphenyl) -3-methylcyclohexane, 6.75 g (0.17 mol) of NaOH and 385 g of water are dissolved in an inert gas atmosphere with stirring . A solution of 1.67 g of the polydimethylsiloxane block (Pn = 71) with bisphenol A end groups (= 5% by weight SiMe₂O) and 0.22 g (2.3 mmol) of phenol in 190 ml of methylene chloride is then added . 15.8 g (0.16 mol) of phosgene were introduced into the well-stirred solution at pH 12 to 13 and 21 to 25 ° C. Then 0.14 ml of ethyl piperidine are added and the mixture is stirred for a further 45 min. The bisphenolate-free aqueous phase is separated off, the organic phase, after acidification with phosphoric acid, washed neutral with water and freed from the solvent.
η rel : 1,279
Tg (DSC): 211.5 ° C
5,33 g (0,0019 Mol) 1,1-Bis-(4-hydroxyphenyl)-3-methyl-cyclohexan, 17,24 g (0,076 Mol) Bisphenol A, 6,75 g (0,17 Mol) NaOH und 385 g Wasser werden in einer Inert-gas-Atmosphäre unter Rühren gelöst. Dann fügt man eine Lösung van 1,37 g des Polydimethylsiloxan-Blocks (Pn = 71) mit Bisphenol A-Endgruppen (= 5 Gew.-% SiMe₂O) und 0,23 g (2,5 mMol) Phenol in 190 ml Methylenchlorid zu. In die gut gerührte Lösung wurden bei pH 12 bis 13 und 21 bis 25°C 15,8 g (0,16 Mol) Phosgen geleitet. Danach werden 0,14 ml Ethylpiperidin zugegeben und noch 45 Min. gerührt. Die bisphenolatfreie wäßrige Phase wird abgetrennt, die organische Phase, nach Ansäuern mit Phosphorsäure, mit Wasser neutral gewaschen und vom Lösungsmittel befreit.
35,72 g (0,094 Mol) 1,1-Bis-(4-hydroxyphenyl)-4-(1,1,3,3-tetramethylbutyl)-cyclohexan, 6,75 g (0,17 Mol) NaOH und 385 g Wasser werden in einer Inertgas-Atmosphäre unter Rühren gelöst. Dann fügt man eine Lösung von 2,20 g des Polydimethylsiloxan-Blocks (Pn = 71) mit Bisphenol A-Endgruppen (= 5 Gew.-% SiMe₂O) und 0,17 g (1,8 mMol) Phenol in 190 ml Methylenchlorid zu. In die gut gerührte Lösung wurden bei pH 12 bis 13 und 21 bis 25°C 15,8 g (0,16 Mol) Phosgen eingeleitet. Danach werden 0,14 ml Ethylpiperidin zugegeben und noch 45 Min. gerührt. Die bisphenolatfreie wäßrige Phase wird abgetrennt, die organische Phase, nach Ansäuern mit Phosphorsäure, mit Wasser neutral gewaschen und vom Lösungsmittel befreit.
ηrel: 1.268
Tg (DSC): 177°C35.72 g (0.094 mol) of 1,1-bis (4-hydroxyphenyl) -4- (1,1,3,3-tetramethylbutyl) cyclohexane, 6.75 g (0.17 mol) of NaOH and 385 g Water is dissolved in an inert gas atmosphere with stirring. A solution of 2.20 g of the polydimethylsiloxane block (Pn = 71) with bisphenol A end groups (= 5% by weight SiMe₂O) and 0.17 g (1.8 mmol) phenol in 190 ml methylene chloride is then added . 15.8 g (0.16 mol) of phosgene were introduced into the well-stirred solution at pH 12 to 13 and 21 to 25 ° C. Then 0.14 ml of ethyl piperidine are added and the mixture is stirred for a further 45 min. The bisphenolate-free aqueous phase is separated off, the organic phase, after acidification with phosphoric acid, washed neutral with water and freed from the solvent.
η rel : 1,268
Tg (DSC): 177 ° C
Claims (3)
R¹, R², R³, R⁴ unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom, C₁-C₈-Alkyl, C₅-C₆-Cycloalkyl, C₆-C₁₀-Aryl und C₇-C₁₂-Aralkyl, bevorzugt Phenyl-C₁-C₄-Alkyl, insbesondere Benzyl,
n 2 oder 3 und
die Reste R⁵ unabhängig voneinander Wasserstoff oder C₁-C₁₂-Alkyl bedeuten, mit der Maßgabe, daß mindestens einer der Reste R⁵ ungleich Wasserstoff ist
mit mittlerem Molekulargewicht
R¹, R², R³, R⁴ independently of one another are hydrogen, halogen, preferably chlorine or bromine, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl and C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl , especially benzyl,
n 2 or 3 and
the radicals R⁵ are independently hydrogen or C₁-C₁₂ alkyl, with the proviso that at least one of the radicals R⁵ is not hydrogen
with medium molecular weight
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3926850A DE3926850A1 (en) | 1989-08-15 | 1989-08-15 | POLYSILOXANE-POLYCARBONATE BLOCK COPOLYMERS BASED ON SPECIAL DIHYDROXYDPHENYLCYCLOALKANE |
| DE3926850 | 1989-08-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0413205A2 true EP0413205A2 (en) | 1991-02-20 |
| EP0413205A3 EP0413205A3 (en) | 1991-07-24 |
Family
ID=6387107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19900114809 Withdrawn EP0413205A3 (en) | 1989-08-15 | 1990-08-02 | Dihydroxydiphenylcycloalkane-based polysiloxane-polycarbonate block copolymers |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5068302A (en) |
| EP (1) | EP0413205A3 (en) |
| JP (1) | JPH0386723A (en) |
| DE (1) | DE3926850A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4118705A1 (en) * | 1991-03-26 | 1993-01-14 | Bayer Ag | STABILIZATION OF HIGH-TEMPERATURE-RESISTANT POLYCARBONATE |
| US5414054A (en) * | 1994-06-01 | 1995-05-09 | Miles Inc. | Copolycarbonate having improved low-temperature impact strength |
| DE19539290A1 (en) * | 1995-10-23 | 1997-04-24 | Bayer Ag | Process for the preparation of poly (diorganosiloxane) -polycarbonate block copolymers |
| US5986019A (en) * | 1997-09-05 | 1999-11-16 | Bayer Corporation | Process for preparing a copolycarbonate |
| US5821321A (en) * | 1997-09-16 | 1998-10-13 | Bayer Corporation | Molding composition having improved impact strength |
| US6727302B2 (en) | 2001-04-03 | 2004-04-27 | General Electric Company | Transparent, fire-resistant polycarbonate |
| US6660787B2 (en) | 2001-07-18 | 2003-12-09 | General Electric Company | Transparent, fire-resistant polycarbonate compositions |
| US6753367B2 (en) | 2001-08-20 | 2004-06-22 | General Electric Company | Flame retardant polycarbonate compositions with improved weathering performance containing cyanoacrylic esters |
| EP3164447B1 (en) | 2014-07-03 | 2019-10-09 | Momentive Performance Materials Inc. | Ester-functional polysiloxanes and copolymers made therefrom |
| WO2016044695A1 (en) | 2014-09-18 | 2016-03-24 | Momentive Performance Materials Inc. | Polysiloxane co-or terpolymers and polymers made therefrom |
| US9334372B1 (en) | 2015-02-25 | 2016-05-10 | Momentive Performance Materials Inc. | Reactive polysiloxanes and copolymers made therefrom |
| WO2023222443A1 (en) | 2022-05-17 | 2023-11-23 | Covestro Deutschland Ag | Polysiloxane-polycarbonate block co-condensates formed from specifically terminated siloxane blocks |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3781378A (en) * | 1971-11-24 | 1973-12-25 | Gen Electric | High temperature membrane materials |
| DE2927937A1 (en) * | 1978-07-21 | 1980-02-07 | Gen Electric | ORGANOPOLYSILOXANE / PHENOLPHTHALEINE / POLYCARBONATE COPOLYMERS |
| EP0164477A1 (en) * | 1984-06-14 | 1985-12-18 | General Electric Company | Polycarbonates exhibiting improved heat resistance |
| EP0193060A2 (en) * | 1985-02-26 | 1986-09-03 | Bayer Ag | Thermoplastic moulding compositions containing polysiloxane-polycarbonate block copolymers |
| EP0193757A1 (en) * | 1985-02-23 | 1986-09-10 | Bayer Ag | Polydiorganosiloxane-polycarbonate block copolymers |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3189662A (en) * | 1961-01-23 | 1965-06-15 | Gen Electric | Organopolysiloxane-polycarbonate block copolymers |
| US3419634A (en) * | 1966-01-03 | 1968-12-31 | Gen Electric | Organopolysiloxane polycarbonate block copolymers |
| JPS58179224A (en) * | 1982-03-18 | 1983-10-20 | Konishiroku Photo Ind Co Ltd | Optical resin composition and optical element |
| DE3334782A1 (en) * | 1983-04-19 | 1984-10-25 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING POLYDIORGANOSILOXANES WITH HYDROXYARYLOXY END GROUPS |
| DE3347071A1 (en) * | 1983-08-31 | 1985-03-14 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS BASED ON POLYSILOXANE-POLYCARBONT BLOCK COPOLYMERS |
-
1989
- 1989-08-15 DE DE3926850A patent/DE3926850A1/en not_active Withdrawn
-
1990
- 1990-08-02 EP EP19900114809 patent/EP0413205A3/en not_active Withdrawn
- 1990-08-08 US US07/564,473 patent/US5068302A/en not_active Expired - Fee Related
- 1990-08-10 JP JP2210559A patent/JPH0386723A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3781378A (en) * | 1971-11-24 | 1973-12-25 | Gen Electric | High temperature membrane materials |
| DE2927937A1 (en) * | 1978-07-21 | 1980-02-07 | Gen Electric | ORGANOPOLYSILOXANE / PHENOLPHTHALEINE / POLYCARBONATE COPOLYMERS |
| EP0164477A1 (en) * | 1984-06-14 | 1985-12-18 | General Electric Company | Polycarbonates exhibiting improved heat resistance |
| EP0193757A1 (en) * | 1985-02-23 | 1986-09-10 | Bayer Ag | Polydiorganosiloxane-polycarbonate block copolymers |
| EP0193060A2 (en) * | 1985-02-26 | 1986-09-03 | Bayer Ag | Thermoplastic moulding compositions containing polysiloxane-polycarbonate block copolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| US5068302A (en) | 1991-11-26 |
| DE3926850A1 (en) | 1991-02-21 |
| EP0413205A3 (en) | 1991-07-24 |
| JPH0386723A (en) | 1991-04-11 |
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